Microbicidal N-(tetrahydro-2-on-fur-3-yl)-N-substituted acetyl-anilines and -naphthylamines

ABSTRACT

Compounds of the formula ##STR1## in which Ar is 2-alkyl-, -alkoxy- or -halo-methyl-phenyl or α-naphthyl, each of which is further substituted, 
     R 1  is 2-furyl, 2-tetrahydrofuryl, alkenyl, cyclopropyl, β-alkoxyethyl, hydroxymethyl, triazolylmethyl, imidazolylmethyl, pyrazolylmethyl, alkylsulfinyl, alkylsulfonyl, alkoxy, alkenyloxy, alkynyloxy, alkylthio, alkenylthio, alkynylthio, alkylsulfinyloxy, dialkylaminosulfinyloxy, phosphoric or thiophosphoric esters or amides, or alkylcarbonyloxy, and 
     R 9  is hydrogen or methyl, 
     are microbicidally, in particular fungicidally active. The preferred compounds are those in which Ar is 2-methylphenyl, 2-methoxyphenyl, 2-chlorophenyl or α-naphthyl, each of which is further substituted by azido, and R 9  is hydrogen.

This is a divisional of application Ser. No. 370,759 filed on Apr. 22, 1982, U.S. Pat. No. 4,448,773.

The present invention relates to microbicidally active acylalanine and acylnaphthylamine derivatives, to processes for producing them, to compositions containing them as active ingredients, and to the use thereof for combating fungi and bacteria.

The novel compounds correspond to the general formula I ##STR2## wherein Ar is a group of the formula ##STR3## R₁ is 2-furyl, 2-tetrahydrofuryl, C₂ -C₄ - alkenyl, cyclopropyl, β-(C₁ -C₄) -alkoxyethyl or --CH₂ Z, each being unsubstituted or substituted by halogen, and Z in the group --CH₂ Z being

(a) --OH,

(b) --1H-1,2,4-triazolyl, 1-imidazolyl or 1-pyrazolyl,

(c) --S(O)_(n) --R₁₃ where R₁₃ is C₁ -C₄ -alkyl, and n is 1 or 2,

(d) --X--R₁₄ where X is oxygen or sulfur, and R₁₄ is C₁ -C₆ -alkyl, C₃ -C₄ -alkenyl or C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy,

(e) --OSO₂ --R₁₅ where R₁₅ is C₁ -C₄ -alkyl, or mono- or di-(C₁ -C₃)-alkylamine, ##STR4## where X is oxygen or sulfur, R₁₆ is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, and R₁₇ is C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, or ##STR5## where R₁₈ is C₁ -C₃ -alkyl which is unsubstituted or substituted by C₁ -C₂ -alkoxy,

R₂ is C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy or halogen,

R₃ is --CH₂ OH, --N₃, ##STR6## where R' is C₁ -C₆ -alkyl or C₂ -C₄ -alkenyl, each unsubstituted or substituted by halogen or C₁ -C₃ -alkoxy, or it is unsubstituted or substituted phenyl, and X is oxygen or sulfur,

R₄ is hydrogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, halogen, --NO₂ or --NH₂,

R₅ is hydrogen or C₁ -C₃ -alkyl,

R₆ is hydrogen or C₁ -C₃ -alkyl, ##STR7## wherein R₇ is hydrogen, C₁ -C₂ -alkyl which is unsubstituted or substituted by halogen, --OH, --OC₁ --C₃ -alkyl or ##STR8## R₈ is C₁ -C₄ -alkyl which is unsubstituted or substituted by C₁ -C₂ -alkoxy,

R₉ is hydrogen or methyl,

R₁₀ is hydrogen or C₁ -C₃ -alkyl,

R₁₁ is C₁ -C₄ -alkyl, whereby R₁₁ 's together can form a C₂ -C₃ -alkylene bridge which is mono- or polysubstituted by C₁ -C₃ -alkyl,

R₁₂ is hydrogen, halogen, C₁ -C₂ -alkyl or phenyl, and

X is oxygen or sulfur.

The substituents R₃, R₄ and R₅ of the naphthylamine derivatives embraced by the formula I fluctuate, so that each of these substituents can occupy the position 2, 3, 4, 5, 6, 7 or 8 in the naphthyl ring.

By alkyl or alkyl moiety of another substituent are meant, depending on the given number of carbon atoms, for example the following groups: methyl, ethyl, propyl and butyl, as well as isomers thereof, such as isopropyl, isobutyl, sec-butyl or tert-butyl. Alkenyl is for example: vinyl, propenyl-(1), allyl, butenyl-(1), butenyl-(2) or butenyl-(3); and alkynyl is particularly propargyl. Halogen here and in the following is fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

A preferred group of microbicides according to the invention comprises compounds of the formula I having the following combination of substituents:

R₁ is 2-furyl, 2-tetrahydrofuryl, C₂ -C₄ -alkenyl, cyclopropyl, β-(C₁ -C₂)-alkoxyethyl or --CH₂ --Z, where Z is

(a) --OH,

(b) 1H-1,2,4-triazolyl or 1-imidazolyl,

(c) --S(O)_(n) --R₁₃, where R₁₃ is C₁ -C₂ -alkyl, and n is 2,

(d) --X'--R₁₄, where X' is oxygen or sulfur, and R₁₄ is C₁ -C₆ -alkyl, C₃ -C₄ -alkenyl or C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy,

(e) --OSO₂ --R₁₅, where R₁₅ is C₁ -C₂ -alkyl, or mono- or di-(C₁ -C₂)-alkylamine, ##STR9## where X" is sulfur, R₁₆ is C₁ -C₂ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₂ -alkylamino, and R₁₇ is C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, or ##STR10## where R₁₈ is C₁ -C₂ -alkyl which is unsubstituted or substituted by C₁ -C₂ -alkoxy,

R₂ is C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy or halogen,

R₃ is --CH₂ OH, --N₃, ##STR11## where R' is C₁ -C₃ -alkyl or C₂ -C₃ -alkenyl, each unsubstituted or substituted by chlorine or methoxy, and X'" is oxygen or sulfur,

R₄ is hydrogen, C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy, --NO₂ or NH₂,

R₅ is hydrogen or C₁ -C₂ -alkyl,

R₆ is hydrogen or C₁ -C₂ -alkyl,

Y has the meanings defined under the formula I, whereby R₇ is hydrogen or C₁ -C₂ -alkyl which is unsubstituted or substituted by halogen, --OH, --O(C₁ -C₂)-alkyl or ##STR12## R₈ is C₁ -C₃ -alkyl which is unsubstituted or substituted by C₁ -C₂ -alkoxy,

R₉ is hydrogen,

R₁₀ is hydrogen or C₁ -C₂ -alkyl,

R₁₁ is C₁ -C₂ -alkyl, whereby R₁₁ 's together can also be C₂ -C₃ -alkylene,

R₁₂ is hydrogen, halogen or C₁ -C₂ -alkyl, and

X is oxygen or sulfur.

A further preferred group of microbicides of the formula I is characterised by the following combination of substituents:

R₁ is 2-furyl, 2-tetrahydrofuryl, C₂ -C₄ -alkenyl, cyclopropyl, β-methoxyethyl or --CH₂ Z, where Z is

(a) 1H-1,2,4-triazolyl,

(b) --S(O)_(n) --R₁₃, where R₁₃ is CH₃, and n is 2,

(c) --X'^(v) --R₁₄, where X'^(v) is oxygen, and R₁₄ is C₁ -C₄ -alkyl, C₃ -C₄ -alkenyl or C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy,

(d) --OSO₂ --R₁₅, where R₁₅ is mono-(C₁ -C₃)-alkylamine, ##STR13## where X^(v) is sulfur, and R₁₆ and R₁₇ independently of one another are each C₁ -C₃ -alkoxy, or ##STR14## where R₁₈ is C₁ -C₃ -alkyl, R₂ is methyl, methoxy or chlorine,

R₃ is --CH₂ OH, --N₃ or ##STR15## R₄ is hydrogen, methyl, methoxy, NO₂ or NH₂, R₅ is hydrogen or methyl,

R₆ is hydrogen or methyl,

Y has the meanings defined under the formula I, whereby

R₇ is C₁ -C₂ -alkyl which is unsubstituted or substituted by chlorine, --OH, --OC₁ --C₂ -alkyl or ##STR16## R₈ is C₁ -C₃ -alkyl, R₉ is hydrogen,

R₁₀ is methyl,

R₁₁ is C₁ -C₂ -alkyl, whereby R₁₁ 's together can also be C₂ -C₃ -alkylene,

R₁₂ is hydrogen, bromine, iodine or C₁ -C₂ -alkyl, and

X is oxygen.

Compounds of the last-mentioned group wherein R₃ is azido (--N₃) are particularly preferred active substances, especially those wherein Y is the group --CH(CH₃)COOCH₃ or ##STR17##

The following individual compounds are to be emphasised on account of their pronounced activity against phytopathogenic microorganisms:

N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2-methyl-6-azido-aniline,

N-(tetrahydro-2'-on-fur-3'-yl)-n-methoxyacetyl-2,6-dimethyl-3-azido-aniline

N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-azido-aniline,

N-(1'-methoxycarbonyl-ethyl)-N-(2-tetrahydrofuryl-carbonyl)-2-methyl-6-azido-aniline,

N-(1'-methoxycarbonyl-3'-hydroxy-n-propyl)-N-methoxyacetyl-2-methyl-6-azido-aniline,

N-(1'-methoxycarbonyl-ethyl)-N-methylaminosulfonylacetyl-2,6-dimethyl-3-azido-aniline,

N-(1'-methoxycarbonyl-3-hydroxy-n-propyl)-N-cyclopropylcarbonyl-2-methyl-6-azido-aniline,

N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2,3-dimethyl-6-azido-aniline,

N-(1'-cyanoethyl)-N-methoxyacetyl-2-methyl-6-azido-aniline,

N-(1'-methyl-2'-dimethoxy-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-azido-aniline,

N-(2'-methyl-3'-methoximino-n-propyl)-N-methoxy-acetyl-2-methyl-6-azido-aniline,

N-(tetrahydro-2'-on-fur-3'-yl)-N-methoxyacetyl-2,3-dimethyl-4-azido-α-naphthylamine,

N-(1'-cyano-ethyl)-N-methoxyacetyl-2,3-dimethyl-4-azido-α-naphthylamine, and

N-(1'-cyanoethyl)-N-(2-tetrahydrofuryl-carbonyl)-2,3-dimethyl-4-azido-.alpha.-naphthylamine.

Phenylacylalanines having microbicidal activity and their production have already been known for some time from the literature. In this connection, there are mentioned for example the following publications: German Offenlegungsschriften Nos. 2,847,287, 2,908,739, 2,920,435, 2,922,759, 2,927,461 and 2,929,525, and also EP 5591, 12 703 and 17 850.

The compounds of the present invention are distinguished by a particularly uniform fungicidal activity, and by properties rendering them especially tolerant to plants.

The compounds of the formula I can be produced in a known manner, for example as described in the following. In the formulae II-VII, the symbols Ar, Y and R₁ -R₆ have the meanings defined under the formula I. The symbol A denotes one of the usual removal groups, for example: alkoxy, benzenesulfonyloxy, p-bromobenzenesulfonyloxy, p-tosyloxy, trifluoroacetoxy, lower-alkylsulfonyloxy, such as mesyloxy, or particularly halogen, such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine.

Production Process

Active substances of the formula I can be produced:

(A) by acylation of compounds of the formula II ##STR18## with carboxylic acids of the formula III or with reactive derivatives thereof; or

(B) by reaction of compounds of the formula IV ##STR19## with compounds of the formula V, wherein A denotes a usual removal group; or, in the case where R₃ is the N₃ group,

(C) by formation of the diazonium salts of the compounds of the formula VI, and subsequent variable reaction as follows: ##STR20## or, in the case where R₃ is the HOCH₂ group,

(D) by reaction of compounds of the formula VII with NaOH in acetone ##STR21## wherein R" is C₁ -C₄ -alkyl; or, in the case where R₃ is one of the groups ##STR22##

(E) by the following reactions of compounds of the formula Ib: ##STR23## wherein "Hal" is halogen, preferably chlorine or bromine. In the case of reactions (a) and (b), they are preferably performed in the presence of an acid-binding agent.

The following reaction conditions are advantageous for the stated production processes:

Process A:

In this process is preferably used a reactive derivative of a compound of the formula III, for example the acid halide or acid anhydride or the ester. The acid chloride or the acid bromide is particularly suitable.

The reaction temperatures are between 0° and 180° C., preferably between 0° and 150° C., or at the boiling point of the solvent or solvent mixture. The use of acid-binding agents or of condensation agents is in some cases advantageous. Suitable as such are organic and inorganic bases, for example tertiary amines, such as trialkylamines (trimethylamine, triethylamine, tripropylamine, and so forth), pyridine and pyridine bases (4-dimethylaminopyridine, 4-pyrrolidylaminopyridine, and the like), oxides and hydroxides, carbonates and hydrogen carbonates of alkali metals and alkaline-earth metals, as well as alkali acetates.

Formed hydrogen halide can in some cases be expelled also by means of the passing through of inert gas, for example nitrogen, from the reaction mixture.

The N-acylation can be performed in the presence of solvents or diluents inert to the reactants. These are for example: aliphatic and aromatic hydrocarbons, such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride and tetrachloroethylene; ethers and ethereal compounds, such as dialkyl ether (diethyl ether, diisopropyl ether, tert-butyl methyl ether, and so forth), anisole, dioxane or tetrahydrofuran; nitriles, such as acetonitrile or propionitrile; N,N-dialkylated amides, such as dimethylformamide or dimethyl sulfoxide; ketones, such as acetone, diethyl ketone, methyl ethyl ketone, and mixtures of solvents of this kind with one another. The acylating agent itself can in some cases serve as solvent. The presence of a reaction catalyst, such as dimethylformamide, can be of advantage in performing acylation.

Process B:

The substituent A in the formula V is in this process one of the customary removal groups, for example alkoxy, benzenesulfonyloxy, p-bromobenzenesulfonyloxy, p-tosyloxy, trifluoroacetyloxy, lower-alkylsulfonyloxy, such as mesyloxy, or it is in particular halogen, such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine. In this embodiment, the starting compound of the formula IV is advantageously firstly converted, with butyllithium or sodium hydride, into the corresponding alkali salt, or alternatively the reaction is carried out in the presence of an acid-binding agent, in a manner analogous to that of variant A, preferably with the addition of catalytic amounts of alkali iodide.

Further methods for synthesis of compounds of the formula I are given for example at the following places in the literature: Houben-Weyl Vol. 11/2, p. 3 and Vol. 8, p.653.

Some of the starting materials for the production of the compounds of the formula I according to the invention are novel, whilst some are known. The novel starting materials can be produced by methods analogous to known methods. Applicable methods in this respect are described for examples at the following places in the literature: J. Org. Chem. 30, 4101 (1965); Tetrahedron 1967, 487; Tetrahedron 1967, 493; Org. Syntheses III, 650; Org. Syntheses III, 652; Org. Syntheses III, 710; and J. Org. Chem. 34, 3430 (1969).

Reference may be made in detail to some methods of production of starting materials. Thus, the starting materials for compounds of the formula I wherein R₃ is an N₃ group can be produced as follows:

nitration of compounds of the formula VIII with a reactive nitrating reagent to give compounds of the formula IX, and subsequent hydrogenation of the nitro compounds with a customary hydrogenating agent to obtain compounds of the formula VI: ##STR24##

The compounds of the formula I contain in the molecule moiety Y at least one asymmetrical carbon atom. Racemates which are produced can be split into the optical antipodes by known methods of splitting racemates. The optical antipodes of the formula I have varying microbicidal activities.

There can be present depending on the manner of substitution further asymmetrical carbon atoms in the molecule of the compounds of the formula I.

Independently of the described optical isomerism in the compounds of the formula I, there is observed an atropisomerism around the aryl--N< axis.

When no specific synthesis is carried out to isolate pure isomers, a product of the formula I is usually obtained as a mixture of these possible isomers.

It has been found that compounds of the formula I surprisingly exhibit a very favourable microbicidal spectrum for practical requirements. They can be used for example to protect cultivated plants.

The main field of application for compounds of the formula I is the combating of harmful microorganisms, particularly phytopathogenic fungi. The compounds of the formula I thus have for practical purposes a very favourable curative, preventive and systemic action for the protection of cultivated plants, without these becoming impaired as a result of undesirable side-effects. Cultivated plants within the scope of the present invention are for example: cereals (wheat, barley, rye, oats and rice); beet: (sugar beet and fodder beet); pomaceous fruit, stone fruit and soft fruit: (apples, pears, plums, peaches, almonds, cherries, strawberries, rasberries and blackberries); legumes: (beans, lentils, peas and soya-bean); oil plants: (rape, mustard, poppy, olives, sunflowers, coco, castor-oil plants, cocoa and groundnuts); Cucurbitacea: (pumpkins, cucumbers and melons); fibre plants: (cotton, flax, hemp and jute); citrus fruits: (oranges, lemons, grapefruit and mandarins); varieties of vegetables: (spinach, lettuce, asparagus, varieties of cabbage, carrots, onions, tomatoes, potatoes and paprika); or plants such as maize, tobacco, nuts, coffee, sugar beet, tea, grapevines, hops, bananas and natural rubber plants; and also ornamental plants.

Microorganisms occurring on plants or on parts of plants (fruit, blossom, foliage, stalks, tubers or roots) of the said crops and of related cultivated crops can be inhibited or destroyed with the active substances of the formula I, and also parts of plants subsequently growing remain preserved from such microorganisms. The active substances are effective against the phytopathogenic fungi belonging to the following classes: against the Peronosporales (Phytophthora, Pythium and Plasmopara) belonging to the Oomycetes class, and also against the Ascomycetes, such as Erysiphe and Venturia pathogens.

Furthermore, the compounds of the formula I have a systemic action. They can also be used as dressing agents for the treatment of seed (fruits, tubers and grain), and of plant cuttings to protect them from fungus infections, and also against phytopathogenic fungi occurring in the soil.

The invention relates therefore also to the use of the compounds of the formula I for combating phytopathogenic microorganisms and/or for preventing infection on plants.

The compounds of the formula I are used either in an unmodified form or preferably together with auxiliaries customarily employed in formulation practice, and are thus processed in a known manner for example into the form of emulsion concentrates, directly sprayable or dilutable solutions, diluted emulsions, wettable powders, soluble powders, dusts or granulates, and also encapsulations in for example polymeric substances. The application processes, such as spraying, atomising, dusting, scattering or pouring, and likewise the type of composition, are selected to suit the objectives to be achieved and the given conditions.

Active substances of the formula I can be applied, simultaneously or successively, with further active substances to the surface or plant to be treated. These active substances can be fertilisers, trace-element agents or other preparations influencing plant growth. They can however also be selective herbicides, insecticides, fungicides, bactericides, nematocides or molluscicides, or mixtures of several of these preparations, optionally together with carriers, surface-active agents or additives facilitating application, which are customarily used in formulation practice.

The formulations, that is to say, the compositions or preparations containing the active substance of the formula I and optionally a solid or liquid additive, are produced in a known manner, for example by the intimate mixing and/or grinding of the active substances with extenders, such as with solvents, solid carriers and optionally surface-active compounds (tensides).

Suitable carriers and additives can be solid or liquid and correspond to the substances commonly used in formulation practice, such as natural or regenerated mineral substances, solvents, dispersing agents, wetting agents, adhesives, thickeners, binders or fertilisers.

Suitable solvents are: aromatic hydrocarbons, preferably the fractions C₈ to C₁₂, such as xylene mixtures or substituted naphthalenes, phthalic esters, such as dibutyl- or dioctylphthalate, aliphatic hydrocarbons, such as cyclohexane or paraffins, alcohols and glycols, as well as ethers and esters thereof, such as ethanol, ethylene glycol, ethylene glycol monomethyl or -ethyl ethers, ketones such as cyclohexanone, strongly polar solvents, such as N-methyl-2-pyrrolidone, dimethylsulfoxide or dimethylformamide, as well as optionally epoxidised vegetable oils, such as epoxidised coconut oil or soybean oil; or water.

The solid carriers used, for example for dusts and dispersible powders, are as a rule natural mineral fillers, such as calcite, talcum, kaolin, montmorillonite or attapulgite. In order to improve the physical properties, it is also possible to add highly dispersed silicic acid or highly dispersed absorbent polymers.

The surface-active agents (tensides) commonly used in formulation practice are described, inter alia, in the following publications: "Mc Cutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ringwood, N.J., 1980; and Sisely and Wood, "Encyclopedia of Surface Active Agents", Chemical Publishing Co., Inc. New York, 1980.

The pesticidal preparations contain as a rule 0.1 to 99, particularly 0.1 to 95, % by weight of active substance of the formula I, 1 to 99% by weight of a solid or liquid additive, and 0 to 25, especially 0.1 to 25, % by weight of a surface-active agent.

Whereas commercial products are preferably in the form of concentrated compositions, the compositions employed by the end-user are as a rule diluted.

The compositions can also contain further additives, such as stabilisers, antifoaming agents, viscosity regulators, binders and adhesives, as well as fertilisers, or other active substances for obtained special effects.

The invention relates also to compositions containing, as at least one active substance, a compound of the formula I, and to the use of the compositions for combating and/or preventing infestation by harmful microorganisms. The present invention embraces also the production of the compositions, this being characterised by the intimate mixing of the active substance with one or more of the substances or groups of substances described herein. Included also is a method of combating harmful microorganisms, which method comprises the application of the compounds of the formula I or of the novel compositions containing them.

The following Examples serve to further illustrate the present invention, without limiting the scope thereof. The temperature values are given in degrees Centigrade; and percentages and parts relate to weight. Except where otherwise stated, the isomeric mixture is meant in all cases where an active substance of the formula I is referred to.

EXAMPLE 1 Production of ##STR25## N-(1'-Methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-acetoxymethylaniline

35.0 g of N-(1'-methoxycarbonyl-ethyl)-2,6-dimethyl-3-acetoxymethylaniline and 13.3 g of sodium carbonate were placed into 250 ml of toluene, and 20.0 g of methoxyacetic acid chloride, dissolved in 50 ml of toluene, were slowly added. After the exothermic reaction had subsided, the temperature was held at 45° C. for 7 hours by means of a water-bath. The cooled reaction mixture was filtered, and the filtrate was concentrated in a rotary evaporator. The oily residue was distilled: b.p. 167°-171° C. at 0.07 bar.

EXAMPLE 2 Production of ##STR26## N-(1'-Methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-hydroxymethylaniline

23.0 g of N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-acetoxymethylaniline, 9.2 g of 30% sodium hydroxide solution and 100 ml of acetone were stirred for 3 hours at room temperature; 20 ml of water were then added, and the reaction mixture was extracted twice with 50 ml of diethyl ether each time. The combined ether extracts were dried over sodium sulfate, and the solvent was evaporated off. The oily crude product was chromatographed through a silica gel column by means of ether/chloroform (1:1) to thus obtain the product in the form of colourless oil: n_(D) ¹⁴ =1.5352.

EXAMPLE 3 Production of ##STR27## N-(1'-Methoxycarbonyl-ethyl)-N-methoxyacetyl-2-methyl-6-azidoaniline

10.0 g of N-(1'-methoxycarbonyl-ethyl)-N-methoxyacetyl-2-methyl-6-aminoaniline were stirred up with 75 g of ice and 15 ml of conc. hydrochloric acid at 0° to 5° C. until a clear solution was formed. At 0° to 5° C. were then added dropwise, within 10 minutes, 2.5 g of sodium nitrite dissolved in 10 ml of water. The reddish-brown solution was stirred for a further 30 minutes at the above temperature, and 100 ml of ether were subsequently added. There was thereupon added dropwise at 0° to 5° C., within 15 minutes, a solution of 2.5 g of sodium azide in 10 ml of water, and the temperature was allowed to rise in the course of 30 minutes to room temperature. The reaction mixture was extracted with ether; the organic phase was then washed with sodium hydrogen carbonate/water, dried with magnesium sulfate, and the solvent was evaporated off. The resulting oil was dried at 40° C. in vacuo; n_(D) ²⁶ :1.5396. n_(D) ²⁸.5 :1.5389.

EXAMPLE 4 Production of ##STR28## N-(1'-Methoxycarbonyl-ethyl)-N-methoxyacetyl-2,6-dimethyl-3-(3',5'-dichlorophenylcarbamoylmethyl)-aniline

16.2 g of N-(1'-methoxycarbonyl-ethyl)-2,6-dimethyl-3-(3',5'-dichlorophenylcarbamoylmethyl)-aniline and 3.2 g of pyridine were placed into 120 ml of toluene; and within 15 minutes were added 4.7 g of methoxyacetic acid chloride, dissolved in 30 ml of toluene. After the exothermic reaction had subsided, stirring was maintained for 4 hours at room temperature, and the reaction suspension was then filtered with suction. The yellow filtrate was washed with water, dried over sodium sulfate, and concentrated in a rotary evaporator. The solid residue was digested with ether, and the white crystals were filtered off with suction; m.p. 126°-128° C.

The following compounds of the formula I were produced in a manner analogous to that described in the foregoing.

                                      TABLE 1.1                                    __________________________________________________________________________     Compounds of the formula                                                        ##STR29##                                                                     Comp.                                                                          No. R.sub.1      R.sub.2 '                                                                          R.sub.3 '    R.sub.6 '                                                                            Y            Physical                  __________________________________________________________________________                                                          data                      1.1.1.                                                                             CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2 OCOCH.sub.3                                                                        CH.sub.3                                                                              ##STR30##   b.p. 167-171°                                                           C./ 0.07 mbar               1.1.2.                                                                           CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2 OH  CH.sub.3                                                                              ##STR31##   n.sub.D.sup.14 =                                                               1.5352                      1.1.3.                                                                           CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           H            N.sub.3                                                                               ##STR32##   n.sub.D.sup.28.5 =                                                             1.5389                      1.1.4.                                                                           CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                            ##STR33##   CH.sub.3                                                                              ##STR34##   m.p. 126-128°                                                           C.                          1.1.5.                                                                           CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR35##   m.p. 99-118°                                                            C.                          1.1.6.                                                                           CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           H            CH.sub.2 OH                                                                           ##STR36##   viscous oil                 1.1.7.                                                                            ##STR37##   CH.sub.3                                                                           CH.sub.2 OCOCH.sub.3                                                                        CH.sub.3                                                                              ##STR38##   viscous oil                 1.1.8.                                                                           CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                            ##STR39##   CH.sub.3                                                                              ##STR40##   viscous oil                 1.1.9.                                                                           CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2 OCOOCH.sub.3                                                                       CH.sub.3                                                                              ##STR41##   n.sub.D.sup.14 =                                                               1.5172                      1.1.10.                                                                           ##STR42##   CH.sub.3                                                                           CH.sub.2 OH  CH.sub.3                                                                              ##STR43##   oil                         1.1.11.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3     N.sub.3                                                                               ##STR44##   m.p. 80-82°                                                             C.                          1.1.12.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR45##   m.p. 88-93°                                                             C.                          1.1.13.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           H            N.sub.3                                                                               ##STR46##                               1.1.14.                                                                           ##STR47##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR48##   oil                         1.1.15.                                                                           ##STR49##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR50##                               1.1.16.                                                                           ##STR51##   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR52##                               1.1.17.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      OCH.sub.3                                                                             ##STR53##                               1.1.18.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR54##                               1.1.19.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           H            N.sub.3                                                                               ##STR55##   yellow oil                  1.1.20.                                                                           ##STR56##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR57##                               1.1.21.                                                                           ##STR58##   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR59##                               1.1.22.                                                                           ##STR60##   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR61##                               1.1.23.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      OCH.sub.3                                                                             ##STR62##                               1.1.24.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      OCH.sub.3                                                                             ##STR63##                               1.1.25.                                                                           ##STR64##   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR65##                               1.1.26.                                                                           ##STR66##   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR67##                               1.1.27.                                                                          CHCH.sub.2   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR68##                               1.1.28.                                                                           ##STR69##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR70##                               1.1.29.                                                                           ##STR71##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR72##                               1.1.30.                                                                           ##STR73##   CH.sub.3                                                                           N.sub.3      OCH.sub.3                                                                             ##STR74##                               1.1.31.                                                                           ##STR75##   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR76##                               1.1.32.                                                                           ##STR77##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR78##                               1.1.33.                                                                           ##STR79##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR80##                               1.1.34.                                                                           ##STR81##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR82##   m.p. 87-92°                                                             C.                          1.1.35.                                                                           ##STR83##   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR84##                               1.1.36.                                                                           ##STR85##   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR86##                               1.1.37.                                                                           ##STR87##   CH.sub.3                                                                           CH.sub.2 OCOCH.sub.3                                                                        CH.sub.3                                                                              ##STR88##                               1.1.38.                                                                          CH.sub.2 SO.sub.2 CH.sub.3                                                                  CH.sub.3                                                                           CH.sub.2 OCOCH.sub.3                                                                        CH.sub.3                                                                              ##STR89##                               1.1.39.                                                                          CH.sub.2 OC.sub.2 H.sub.5                                                                   CH.sub.3                                                                           H            N.sub.3                                                                               ##STR90##                               1.1.40.                                                                           ##STR91##   CH.sub.3                                                                            N.sub.3     CH.sub.3                                                                              ##STR92##                               1.1.41.                                                                           ##STR93##   CH.sub.3                                                                           CH.sub.2 OCOCH.sub.3                                                                        CH.sub.3                                                                              ##STR94##                               1.1.42.                                                                          CH.sub.2 OCH.sub.2CHCH.sub.2                                                                CH.sub.3                                                                           CH.sub.2 OCOCH.sub.3                                                                        CH.sub.3                                                                              ##STR95##                               1.1.43.                                                                          CH.sub.2 OCH.sub.2CHCH.sub.2                                                                CH.sub.3                                                                           H            N.sub.3                                                                               ##STR96##                               1.1.44.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR97##                               1.1.45.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3     N.sub.3                                                                               ##STR98##                               1.1.46.                                                                           ##STR99##   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR100##  m.p. 117-120°                                                           C.                          1.1.47.                                                                          CH.sub.2 OC.sub.2 H.sub.5                                                                   CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR101##                              1.1.48.                                                                          CH.sub.2 OCH.sub.3                                                                          Cl  H            N.sub.3                                                                               ##STR102##                              1.1.49.                                                                           ##STR103##  CH.sub.3                                                                           CH.sub.3     N.sub.3                                                                               ##STR104##                              1.1.50.                                                                           ##STR105##  CH.sub.3                                                                           CH.sub.3     N.sub.3                                                                               ##STR106##                              1.1.51.                                                                           ##STR107##   CH.sub.3                                                                          H            N.sub.3                                                                               ##STR108##                              1.1.52.                                                                           ##STR109##  CH.sub.3                                                                           H            N.sub.3                                                                               ##STR110##                              1.1.53.                                                                          CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR111##                              1.1.54.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           H            N.sub.3                                                                               ##STR112##                              1.1.55.                                                                           ##STR113##  CH.sub.3                                                                           H            N.sub.3                                                                               ##STR114##                              1.1.56.                                                                           ##STR115##  CH.sub.3                                                                           H            N.sub.3                                                                               ##STR116##                              1.1.57.                                                                           ##STR117##  CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR118##                              1.1.58.                                                                          CH.sub.2 OCOCH.sub.3                                                                        CH.sub.3                                                                           H            N.sub.3                                                                               ##STR119##                              1.1.59.                                                                          CH.sub.2 CH.sub.2 OCH.sub.3                                                                 CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR120##                              1.1.60.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR121##                              1.1.61.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR122##                              1.1.62.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           H            N.sub.3                                                                               ##STR123##                              1.1.63.                                                                           ##STR124##  CH.sub.3                                                                           H            N.sub.3                                                                               ##STR125##                              1.1.64.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           H            N.sub.3                                                                              CH.sub.2CCH                            1.1.65.                                                                            CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                             CH.sub.3CCJ                              1.1.66.                                                                           ##STR126##  CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR127##                              1.1.67.                                                                          CHCHCH.sub.3 CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                              ##STR128##                              1.1.68.                                                                           ##STR129##  CH.sub.3                                                                           N.sub.3      CH.sub.3                                                                             CH.sub.2CCCH.sub.3                       1.1.69.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2 OH  CH.sub.3                                                                              ##STR130##                              1.1.70.                                                                          CH.sub.2 OC.sub.2 H.sub.5                                                                   CH.sub.3                                                                           CH.sub.2 OH  CH.sub.3                                                                              ##STR131##                              1.1.71.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2 OH  CH.sub.3                                                                              ##STR132##                              1.1.72.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.3     CH.sub.2 OH                                                                           ##STR133##                              1.1.73.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2 OH  CH.sub.3                                                                              ##STR134##                              1.1.74.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2 OH  CH.sub.3                                                                              ##STR135##                              1.1.75.                                                                          CH.sub.2 OCH.sub.3                                                                          CH.sub.3                                                                           CH.sub.2 OH  CH.sub.3                                                                              ##STR136##                              1.1.76.                                                                          CH.sub.2 OCH.sub.3                                                                          Cl  H            CH.sub.2 OH                                                                           ##STR137##                            __________________________________________________________________________

                                      TABLE 1.2                                    __________________________________________________________________________      ##STR138##                                                                    Comp.                                                                          No. R.sub.1  R.sub.2 '                                                                          R.sub.3 '                                                                          R.sub.4 '                                                                         R.sub.5 '                                                                          R.sub.6 '                                                                          Y           Physical data                      __________________________________________________________________________     1.2.1.                                                                             CH.sub.2 OCH.sub.3                                                                      CH.sub.3                                                                           CH.sub.3                                                                           N.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            ##STR139##                                      1.2.2.                                                                           CH.sub.2 Oi-C.sub.3 H.sub.7                                                             CH.sub.3                                                                           CH.sub.3                                                                           N.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            ##STR140##                                      1.2.3.                                                                           CH.sub. 2 OCH.sub.3                                                                     CH.sub.3                                                                           CH.sub.3                                                                           N.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            ##STR141##                                      1.2.4.                                                                            ##STR142##                                                                             CH.sub.3                                                                           CH.sub.3                                                                           N.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            ##STR143##                                      1.2.5.                                                                           CH.sub.2 SO.sub.2 CH.sub.3                                                              CH.sub.3                                                                           CH.sub.3                                                                           N.sub.3                                                                           CH.sub.3                                                                           CH.sub.3                                                                            ##STR144##                                    __________________________________________________________________________

                  TABLE 2.1                                                        ______________________________________                                          ##STR145##                                                                                                             Phys-                                 Comp.                        ical                                              No.                                                                              R.sub.3 '                                                                              R.sub.5 '    Y     data                                              ______________________________________                                         2.1.1.                                                                               N.sub.3      H                                                                                       ##STR146## resin                                     2.1.2.                                                                             CH.sub.3     N.sub.3                                                                                 ##STR147##                                           2.1.3.                                                                             N.sub.3      H                                                                                       ##STR148##                                           2.1.4.                                                                             CH.sub.2 OH  H                                                                                       ##STR149##                                           2.1.5.                                                                             CH.sub.3     N.sub.3                                                                                 ##STR150##                                           2.1.6.                                                                             N.sub.3      H                                                                                       ##STR151##                                           2.1.7.                                                                             CH.sub.3     N.sub.3                                                                                 ##STR152##                                           2.1.8.                                                                             CH.sub.2 OCOCH.sub.3                                                                        NO.sub.2                                                                                ##STR153##                                           2.1.9.                                                                             CH.sub.3     N.sub.3                                                                                 ##STR154##                                           2.1.10.                                                                            N.sub.3      H                                                                                       ##STR155##                                         ______________________________________                                    

                  TABLE 2.2                                                        ______________________________________                                          ##STR156##                                                                        Comp.                                                                      No. Y         Physical data                                                    ______________________________________                                         2.2.1.                                                                                    ##STR157##                                                            2.2.2.                                                                                  ##STR158##      m.p. 45-57° C.                                 2.2.3.                                                                                  ##STR159##                                                            2.2.4.                                                                                  ##STR160##                                                            2.2.5.                                                                                  ##STR161##                                                            2.2.6.                                                                                  ##STR162##                                                            2.2.7.                                                                                  ##STR163##                                                          ______________________________________                                    

                  TABLE 2.3                                                        ______________________________________                                          ##STR164##                                                                    Comp.                                                                          No.      R.sub.1           Physical data                                       ______________________________________                                         2.3.1.   CH.sub.2 OC.sub.2 H.sub.5                                                                        m.p. 93-96° C.                                 2.3.2.                                                                                 ##STR165##                                                             2.3.3.                                                                                 ##STR166##                                                             2.3.4.                                                                                 ##STR167##                                                             2.3.5. CH.sub.2 OSO.sub.2 NHCH.sub.3                                         2.3.6.   CH.sub.2 SO.sub.2 CH.sub.3                                            2.3.7.   CH.sub.2 CH.sub.2 OCH.sub.3                                           ______________________________________                                    

                  TABLE 2.4                                                        ______________________________________                                          ##STR168##                                                                        Comp. No.  Y'             Physical data                                    ______________________________________                                         2.4.1.     CH.sub.2 CN    wax-like substance                                   2.4.2.     CH.sub.2 CH(OCH.sub.3).sub.2                                                                  viscous oil                                          2.4.3.     CH.sub.2 CCH   m.p. 57-63° C.                                ______________________________________                                    

BIOLOGICAL EXAMPLES

The compositions used in the following Examples are formulated in the manner described in the subsequent formulation examples.

EXAMPLE 5 Action against Phytophthora infestans on tomato plants

(a) Residual protective action

After 3-weeks' cultivation, tomato plants were sprayed with a spray liquor produced from wettable powder of the active substance (0.02% of active substance). After 24 hours, the treated plants were infested with a suspension of sporangia of the fungus. An assessment of the fungus infection was made after incubation of the infested plants during 5 days at 20° C. with 90-100% relative humidity.

Compared with the fungus infection occurring on the control plants (100% infection), the infection on tomato plants treated with any one of the compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.4, 1.1.5, 1.1.7, 1.1.9, 1.1.10, 1.1.12, 1.1.14, 1.1.19, 1.1.34, 1.1.61 and 1.1.62, and Nos. 2.2.1, 2.2.2 and 2.2.3 was reduced to less than 10%.

(b) Systemic action

A spray liquor prepared from wettable powder of the active substance (0.006% of active substance, relative to the volume of soil) was applied to the soil in which tomato plants had been cultivated for 3 weeks. Care was taken to ensure that the spray liquor did not come into contact with the parts of the plants above the soil. After 48 hours, the treated plants were infested with a suspension of sporangia of the fungus. An assessment of fungus infection was made after incubation of the infested plants during 5 days at 20° C. with 90-100% relative umidity.

Compounds exhibiting in the above test a very good systemic action were, inter alia: Compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.5, 1.1.9, 1.1.10, 1.1.12, 1.1.14, 1.1.19, 1.1.34, 1.1.54 and 1.1.61, and also No. 2.2.1 and No. 2.2.2. Compared with fungus infection occuring on the untreated but infested control plants (100% infection), the infection on tomato plants treated with any one of the these compounds had been almost completely eliminated (0 to 5%).

(c) Residual curative action

After 3-weeks' cultivation, tomato plants were infested with a suspension of sporangia of the fungus. After an incubation time of 22 hours in a moist chamber at 20°C. with 90°-100° relative humidity, the infested plants were dried, and then sprayed with a spray liquor prepared from wettable powder of the active substance (0.06% of active substance). After the drying of the applied coating, the treated plants were returned to the moist chamber. An assessment of fungus infection was made 5 days after infestation.

Compared with fungus infection occurring on the untreated but infested control plants (100% infection), the infection on tomato plants treated with any one of the Compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.10, 1.1.12, 1.1.14, 1.1.19, 1.1.34 and 1.1.61 and Nos. 2.2.1, 2.2.2 and 2.2.3 was less than 10%.

EXAMPLE 6 Residual protective action against Venturia inaequalis on apple shoots

Apple seedlings having 10-20 cm long fresh shoots were sprayed with a spray liquor prepared from wettable powder of the active substance (0.06% of active substance). The treated plants were sprayed after 24 hours with a conidiospore suspension of the fungus. The plants were then incubated for 5 days with 90-100% relative humidity, and for a further 10 days they were kept at 20°-24° C. in a greenhouse. The extent of scab infection was assessed 15 days after infestation. The occurrence of the disease was reduced to 10 to 15% by, inter alia: the compounds Nos. 1.1.1, 1.1.2, 1.1.10, 1.1.37, 1.1.42, 1.1.69, 2.1.1, 2.1.4 and 2.1.8.

EXAMPLE 7 Action against Pythium debaryanum on sugar beet plants

(a) Effect after soil application

The fungus was cultivated on a carrot-chips nutrient solution, and was then added to a soil/sand mixture. The soil infested in this manner was placed into flower pots, and sown with sugar-beet seeds. Immediately after the sowing, the test preparation prepared from wettable powder was poured, as an aqueous suspension, over the soil (20 ppm of any one of the compounds in the Tables 1 and 2, relative to the volume of soil). Th pots were then placed for 2-3 weeks in a greenhouse at about 20° C. The soil was maintained during this period uniformly moist by light watering. In the evaluation of the test, the sprouting of the sugar-beet plants and the proportion of healthy plants and of diseased plants were assessed.

(b) Effect after dressing application

The fungus was cultivated on a carrot-chips nutrient solution, and applied to a soil/sand mixture. The soil infested in this manner was placed into soil trays, and sown with sugar-beet seeds which had been dressed with the test preparations formulated as dressing powder (0.06% of any one of the compounds in Tables 1 and 2). The sown trays were left for 2-3 weeks in a greenhouse at about 20+ C. The soil was maintained uniformly moist by light spraying. In the assessment of the test results, the extent of sprouting of the sugar-beet plants was determined.

The compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.5, 1.1.7, 1.1.9, 1.1.10, 1.1.12, 1.1.14, 1.1.19, 1.1.25, 1.1.34, 1.1.54, 1.1.61 and 1.1.62 and Nos. 2.2.1, 2.2.2 and 2.2.3 were completely effective against Pythium pathogens (over 90% of plants had sprouted) in both tests (a) and (b). The plants had a healthy appearance.

An equally good effect was achieved in analogous tests against Phythium pathogens on maize plants.

EXAMPLE 8 Action against Podosphaera leucotricha on apple seedlings Residual protective action

Apple seedlings having about 5 developed leaves were sprayed with a spray liquor prepared from wettable powder of the active substance (0.06% of active substance). After 24 hours, the treated plants were infested with a conidiospore suspension of the fungus, and were transferred to a controlled atmosphere chamber at 20° with 70% relative humidity. The assessment of fungus infection was made 12 days after infestation.

Compared with fungus infection occurring on the untreated but infested apple seedings (100% infection), the infection on apple seedlings treated with any one of the compounds Nos. 1.1.1, 1.1.2, 1.1.3, 1.1.4, 1.1.5, 1.1.7, 1.1.9, 1.1.10, 1.1.14, 1.1.19, 1.1.25, 1.1.34, 1.1.54, 1.1.61, and 1.1.62 and Nos. 2.2.1, 2.2.2 and 2.2.3 was less than 10%.

    ______________________________________                                         Formulation examples for liquid active substances                              of the formula I (% = percent by weight)                                       Example 9 Emulsion concentrates                                                                   (a)      (b)    (c)                                         ______________________________________                                         active substance   25%      40%    50%                                         from Tables 1.1-2.4                                                            calcium dodecylbenzenesulfonate                                                                    5%       8%     6%                                         castor oil-polyethylene glycol                                                                     5%      --     --                                          ether (36 mols of ethylene oxide)                                              tributylphenol-polyethylene glycol                                                                --       12%     4%                                         ether (30 mols of ethylene oxide)                                              cyclohexanone      --       15%    20%                                         xylene mixture     65%      25%     20%.                                       ______________________________________                                    

Emulsions of any required concentration can be produced from such concentrates by dilution with water.

    ______________________________________                                         Example 10 Solutions                                                                              (a)     (b)    (c)   (d)                                    ______________________________________                                         active substance   80%     10%    5%    95%                                    from Tables 1.1-2.4                                                            ethylene glycol-monomethyl ether                                                                  20%     --     --    --                                     polyethylene glycol MG 400                                                                        --      70%    --    --                                     N--methyl-2-pyrrolidone                                                                           --      20%    --    --                                     epoxidised coconut oil                                                                            --      --     1%     5%                                    ligroin (boiling limits 160-190° C.)                                                       --      --     94%    --.                                   ______________________________________                                    

The solutions are suitable for application in the form of very fine drops.

    ______________________________________                                         Example 11 Granulates  (a)     (b)                                             ______________________________________                                         active substance from Tables 1.1-2.4                                                                  5%      10%                                             kaolin                 94%     --                                              highly dispersed silicic acid                                                                         1%      --                                              attapulgite            --       90%.                                           ______________________________________                                    

The active substance is dissolved in methylene chloride, the solution is sprayed onto the carrier, and the solvent is subsequently evaporated off in vacuo.

    ______________________________________                                         Example 12 Dusts       (a)     (b)                                             ______________________________________                                         active substance from Tables 1.1-2.4                                                                  2%      5%                                              highly dispersed silicic acid                                                                         1%      5%                                              talcum                 97%     --                                              kaolin                 --      90%.                                            ______________________________________                                    

Ready-for-use dusts are obtained by the intimate mixing together of the carriers with the active substance.

    ______________________________________                                         Formulation examples for solid active substances of                            the formula I (% = percent by weight)                                          Example 13 Wettable powders                                                                         (a)      (b)    (c)                                       ______________________________________                                         active substance from Tables 1.1-2.4                                                                25%      50%    75%                                       sodium lignin sulfonate                                                                             5%        5%    --                                        sodium lauryl sulfate                                                                               3%       --      5%                                       sodium diisobutylnaphthalene sulfonate                                                              --        6%    10%                                       octylphenolpolyethylene glycol ether                                                                --        2%    --                                        (7-8 mols of ethylene oxide)                                                   highly dispersed silicic acid                                                                       5%       10%    10%                                       kaolin               62%      27%    --                                        ______________________________________                                    

The active substance is well mixed with the additives and the mixture is thoroughly ground in a suitable mill. Wettable powders which can be diluted with water to give suspensions of the required concentration are obtained.

    ______________________________________                                         Example 14 Emulsion concentrate                                                ______________________________________                                         active substance from Tables 1.1-2.4                                                                  10%                                                     octylphenolpolyethylene glycol ether                                                                  3%                                                      (4-5 mols of ethylene oxide)                                                   calcium dodecylbenzenesulfonate                                                                       3%                                                      castor oil polyglycol ether                                                                           4%                                                      (36 mols of ethylene oxide)                                                    cyclohexanone          30%                                                     xylene mixture         50%.                                                    ______________________________________                                    

Emulsions of the required concentration can be obtained from this concentrate by dilution with water.

    ______________________________________                                         Example 15 Dusts       (a)    (b)                                              ______________________________________                                         active substance from Tables 1.1-2.4                                                                   5%    8%                                               talcum                 95%    --                                               kaolin                 --     92%.                                             ______________________________________                                    

Dusts ready for use are obtained by mixing the active substance with the carriers and grinding the mixture in a suitable mill.

    ______________________________________                                         Example 16 Extruder granulate                                                  ______________________________________                                         active substance from Tables 1.1-2.4                                                                  10%                                                     sodium lignin sulfonate                                                                               2%                                                      carboxymethylcellulose 1%                                                      kaolin                 87%.                                                    ______________________________________                                    

The active substance is mixed and ground with the additives, and the mixture is moistened with water. This mixture is then extruded and dried in a stream of air.

    ______________________________________                                         Example 17 Coated granulate                                                    ______________________________________                                         active substance from Tables 1.1-2.4                                                                  3%                                                      polyethylene glycol (MG 200)                                                                          3%                                                      kaolin                 94%.                                                    ______________________________________                                    

The finely ground active substance is evenly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Dustfree coated granules are obtained in this manner.

    ______________________________________                                         Example 18 Suspension concentrate                                              ______________________________________                                         active substance from Tables 1.1-2.4                                                                     40%                                                  ethylene glycol           10%                                                  nonylphenolpolyethylene glycol                                                                            6%                                                  ether (15 mols of ethylene oxide)                                              sodium lignin sulfonate   10%                                                  carboxymethyl cellulose    1%                                                  37% aqueous formaldehyde solution                                                                         0.2%                                                silicone oil in the form of a                                                                             0.8%                                                75% aqueous emulsion                                                           water                     32%.                                                 ______________________________________                                    

The finely ground active substance is intimately mixed with the additives. There is thus obtained a suspension concentrate from which can be prepared, by dilution with water, suspensions of the concentration required. 

What is claimed is:
 1. A compound of the formula I ##STR169## wherein Ar is a group of the formula ##STR170## R₁ is 2-furyl, 2-tetrahydrofuryl, C₂ -C₄ -alkenyl, cyclopropyl, β-(C₁ -C₄)-alkoxyethyl or --CH₂ Z, each being unsubstituted or substituted by halogen, and Z being(a) --OH, (b) --1H-1,2,4-triazolyl, 1-imidazolyl or 1-pyrazolyl, (c) --S(O)_(n) --R₁₃, where R₁₃ is C₁ -C₄ -alkyl, and n is 1 or 2, (d) --X--R₁₄, where X is oxygen or sulfur, and R₁₄ is C₁ -C₆ -alkyl, C₃ -C₄ -alkenyl or C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy, (e) --OSO₂ --R₁₅, where R₁₅ is C₁ -C₄ -alkyl, or mono- or di-(C₁ -C₃)-alkylamine, ##STR171## where X is oxygen or sulfur, R₁₆ is C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, and R₁₇ is C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, or ##STR172## where R₁₈ is C₁ -C₃ -alkyl which is unsubstituted or substituted by C₁ -C₂ -alkoxy, R₂ is C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy or halogen, R₃ is --CH₂ OH, --N₃, ##STR173## where R' is C₁ -C₆ -alkyl or C₂ -C₄ -alkenyl, each unsubstituted or substituted by halogen or C₁ -C₃ -alkoxy, or it is phenyl substituted by chlorine and X is oxygen or sulfur, R₄ is hydrogen, C₁ -C₃ -alkyl, C₁ -C₃ -alkoxy, halogen, --NO₂ or --NH₂, R₅ is hydrogen or C₁ -C₃ -alkyl, R₆ is hydrogen or C₁ -C₃ -alkyl, R₉ is hydrogen or methyl, X is oxygen or sulfur.
 2. A compound according to claim 1, whereinR₁ is 2furyl, 2-tetrahydrofuryl, C₂ -C₄ -alkenyl, cyclopropyl, β-(C₁ -C₂)-alkoxyethyl or CH₂ --Z, where Z is(a) --OH, (b) 1H-1,2,4-triazolyl or 1-imidazolyl, (c) --S(O)_(n) --R₁₃, where R₁₃ is C₁ -C₂ -alkyl, and n is 2, (d) --X'--R₁₄, where X' is oxygen or sulfur, and R₁₄ is C₁ -C₆ -alkyl, C₃ -C₄ -alkenyl or C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy, (e) --OSO₂ --R₁₅, where R₁₅ is C₁ -C₂ -alkyl, or mono, or di-(C₁ -C₂)-alkylamine, ##STR174## where X" is sulfur, R₁₆ is C₁ -C₂ -alkyl, C₁ -C₄ -alkoxy or C₁ -C₂ -alkylamino, and R₁₇ is C₁ -C₄ -alkoxy or C₁ -C₄ -alkylamino, or ##STR175## where R₁₈ is C₁ -C₂ -alkyl which is unsubstituted or substituted by C₁ -C₂ -alkoxy, R₂ is C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy or halogen, R₃ is --CH₂ OH, --N₃, ##STR176## where R' is C₁ -C₃ -alkyl or C₂ -C₃ -alkenyl, each unsubstituted or substituted by chlorine or methoxy, and X"' is oxygen or sulfur, R₄ is hydrogen, C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy, --NO₂ or --NH₂, R₅ is hydrogen or C₁ -C₂ -alkyl, R₆ is hydrogen or C₁ -C₂ -alkyl, R₉ is hydrogen.
 3. A compound according to claim 2, whereinR₁ is 2-furyl, 2-tetrahydrofuryl, C₂ -C₄ -alkenyl, cyclopropyl, 4-methoxyethyl or --CH₂ Z, where Z is(a) 1H-1,2,4-triazolyl, (b) --S(O)_(n) --R₁₃, where R₁₃ is CH₃, and n is 2, (c) --X'^(v) --R₁₄, where X'^(v) is oxygen, and R₁₄ is C₁ -C₄ -alkyl, C₃ -C₄ -alkenyl or C₃ -C₄ -alkynyl, each unsubstituted or substituted by C₁ -C₂ -alkoxy, (d) --OSO₂ --R₁₅, where R₁₅ is mono-(C₁ -C₃)-alkylamine, ##STR177## where X^(v) is sulfur, and R₁₆ and R₁₇ independently of one another are each C₁ -C₃ -alkoxy, or ##STR178## where R₁₈ is C₁ -C₃ -alkyl, R₂ is methyl, methoxy or chlorine, R₃ is --CH₂ OH, --N₃ or ##STR179## R₄ is hydrogen, methyl, methoxy, NO₂ or NH₂, R₅ is hydrogen or methyl, R₆ is hydrogen or methyl, R₉ is hydrogen, X is oxygen.
 4. A compound according to claim 3, wherein R₃ is the azido group (--N₃).
 5. A compound according to claim 4, selected from the group of the following azido compounds:N-(tetrahydro-2'-on-fur-3'-yl)-N-methoxyacetyl-2,6-dimethyl-3azido-aniline, and N-(tetrahydro-2'-on-fur3'-yl)-N-methoxyacetyl-2,3-dimethyl-4-azido-α-naphthylamine.
 6. A composition for combating and/or preventing an infestation by harmful microorganisms, which composition contains as active ingredient at least one active substance according to claim 1 and an inert carrier.
 7. A composition according to claim 6, which contains 0.1 to 99 percent by weight of the active substance 1 to 99 percent by weight of additives, and 0 to 25 percent by weight of a surface-active agent.
 8. A composition according to claim 7, which contains 0.1 to 95 percent by weight of the active substance.
 9. A composition according to claim 8, which contains 0.1 to 25 percent by weight of a surface-active agent.
 10. A process for combating and/or preventing an infestation of plants by phytopathogenic microorganisms, which process comprises applying an effective amount of a compound according to any one of claims 1 to 4 and 5, in diluted form, to the plants or to the locus thereof.
 11. A process for combating and/or preventing an infestation of plants by phytopathogenic fungi, which process comprises applying a fungicidally effective amount of a compound according to any one of claims 1 to 4 and 5, in diluted form, to the plants or to the locus thereof. 